JP5662794B2 - Water-in-oil emulsion composition - Google Patents

Description

  The present invention relates to the technical field of water-in-oil emulsion compositions.

Poly (12-hydroxystearic acid) esters of polyhydric alcohols can be used to prepare low-viscosity cosmetics and themselves do not stick to the light feel, so anyway they tend to be greasy and heavy to use. Widely used as an emulsifier in emulsified compositions.
However, the characteristic “low viscosity” sometimes impairs the stability at high temperature, and sometimes the dosage form cannot be varied, resulting in a monotonous product.
In general, it is known to add a hydrophilic or lipophilic thickener to increase the viscosity of the composition, and water-in-oil using a poly (12-hydroxystearic acid) ester of a polyhydric alcohol. It is also blended in the mold emulsion composition.
For example, a technique of combining polyoxyethylene dipolyhydroxystearate and 1,1-methylene-bis (4-isocyanatecyclohexane) polypropylene glycol copolymer is disclosed (Patent Document 1: Japanese Patent Application Laid-Open No. 2002-308962). Publication). However, since 1,1-methylene-bis (4-isocyanatecyclohexane) polypropylene glycol copolymer forms a film on the applied skin, the viscosity of the composition increases, but the usability may be deteriorated.
In addition, it is known that when an electrolyte is blended in a water-in-oil emulsion composition, stability is improved (Patent Document: JP-A-2003-286125). However, the effect of increasing the viscosity is low in the electrolyte, and the blending of the electrolyte was an auxiliary means.
In general, the viscosity of a liquid varies greatly depending on the temperature. However, the small change in viscosity with respect to the temperature change is not affected by the environment (low or high outside temperature) during use, and is always constant. This is preferable.
There is a need for a technique for increasing the viscosity of a water-in-oil emulsion composition using a poly (12-hydroxystearic acid) ester of a polyhydric alcohol and producing a composition having a small viscosity change with respect to a temperature change.

JP 2002-308962 A JP 2003-286125 A

  It is an object to increase the viscosity of a water-in-oil emulsion composition using a poly (12-hydroxystearic acid) ester of a polyhydric alcohol.

The main configuration of the present invention is as follows.
(1) A water-in-oil emulsion composition comprising PEG-30 dipolyhydroxystearate as the component (A) and sodium tocopheryl phosphate as the component (B).
(2) The water-in-oil emulsion composition according to ( 1) , further comprising a chelating agent as the component (C).
(3) The viscosity measured by stirring for 30 seconds at a measurement temperature of 25 ° C. in a B-type viscometer, No. 4 rotor, 12 rpm, 12 seconds is in the range of 5000 to 22000 mPa · s, as described in (1) or (2) A water-in-oil emulsion composition.
(3) The blending amount of component (A) dipolyhydroxystearic acid PEG-30 is 0.1 to 5% by weight, and the blending amount of component (B) sodium tocopheryl phosphate is 0.1 to 10% by weight. The water-in-oil emulsion composition according to any one of (1) to ( 3) .

By including sodium tocopheryl phosphate in a water-in-oil emulsion composition emulsified with poly (12-hydroxystearic acid) ester of polyhydric alcohol, the viscosity of the composition can be significantly increased. . Therefore, the formulation of the water-in-oil emulsion composition emulsified with poly (12-hydroxystearic acid) ester of polyhydric alcohol can be easily varied.
That is, while maintaining a refreshing and non-sticky feeling, it is possible to increase the viscosity and realize a high-grade creamy feeling when applying the preparation.
The water-in-oil emulsion composition of the present invention is excellent in storage stability.
The difference in the viscosity at each storage temperature (5 ° C. to 50 ° C.) of the water-in-oil emulsion composition having the configuration of the present invention is a level with no problem in terms of quality when commercialized.
Furthermore, by arbitrarily containing a chelating agent, it is possible to significantly reduce the difference in viscosity depending on the storage temperature.
Therefore, it is possible to provide a skin external preparation having a constant feeling of use (viscosity) without being affected by the environment during use (the outside air temperature is low or high). The water-in-oil emulsified composition of the present invention has an excellent feeling of use without being stiff.

The poly (12-hydroxystearic acid) ester of the polyhydric alcohol which is the component (A) of the present invention is prepared by adding a halogenating agent such as thionyl chloride to the poly (12-hydroxystearic acid) in the presence of alkali. It can be obtained by reacting acid chloride prepared by reaction.
Preferred examples of the polyhydric alcohol include propylene glycol, butanediol, pentanediol, (poly) glycerin, (poly) propylene glycol, and polyethylene glycol, with polyethylene glycol being particularly preferred. In this case, the polyethylene glycol preferably has an average molecular weight of 400 to 6000. On the other hand, the poly (12-hydroxystearic acid) serving as a hydrophobic group preferably has an average molecular weight of 1000 to 3000.
It is preferable to use di (12-hydroxystearic acid) ester of polyethylene glycol, and those whose INCI name is listed as dipolyhydroxystearic acid PEG-30 are preferable. 135, Cisroll DPHS manufactured by Croda Japan Co., Ltd., and the like.
The blending amount of the poly (12-hydroxystearic acid) ester of the polyhydric alcohol which is the component (A) of the present invention is preferably from 0.1 to 5% by mass, particularly preferably from 1 to 5% by mass. If it is less than 0.1% by mass, emulsification may be insufficient. If it exceeds 5 mass%, a sticky feeling may be obtained.

The tocopheryl sodium phosphate which is the component (B) of the present invention is a sodium salt of a phosphate ester of tocopherol (vitamin E). It is a white to slightly yellow powder and easily dissolves in water at room temperature. The solution has a pH of 9.0 to 10.0 in a 2% by mass aqueous solution and a viscosity of 100 mPa · s or less (B-type viscometer, No. 1 rotor, 12 rpm, 30 seconds, measured at 25 ° C.).
Vitamin E is a useful vitamin as a fat-soluble vitamin, and has the function of protecting the skin from oxidative stress caused by ultraviolet rays in cooperation with water-soluble antioxidant compounds such as vitamin C. Sodium tocopheryl phosphate is derivatized because vitamin E itself is chemically unstable. Sodium tocopheryl phosphate is converted into vitamin E by dephosphorylating enzyme in the skin, and it exhibits antioxidant and anti-inflammatory effects to improve rough skin. It is blended in an external preparation.
Commercially available “Vitamin E sodium phosphate” manufactured by Showa Denko KK can be used.
In the present invention, sodium tocopheryl phosphate not only exhibits a cosmetic effect, but also functions to adjust the viscosity of a water-in-oil emulsion composition emulsified with a poly (12-hydroxystearic acid) ester of a polyhydric alcohol. To do. This is a unique phenomenon.
In order to increase the viscosity of the water-in-oil emulsion composition emulsified with poly (12-hydroxystearic acid) ester of polyhydric alcohol, 0.1 to 10% by mass is contained with respect to the water-in-oil emulsion composition. It is preferable to contain 0.5 to 6% by mass.
If it is less than 0.1% by mass, it may not be able to sufficiently contribute to the thickening effect of the emulsion composition of the present invention. When it exceeds 10 mass%, it is uneconomical.

  The viscosity of the water-in-oil emulsion composition of the present invention is preferably in the range of 5000 to 22000 mPa · s (B-type viscometer, No. 4 rotor, 12 rpm, 30 seconds, 25 ° C. measurement).

It is preferable to add a chelating agent as the component (C) to the water-in-oil emulsion composition of the present invention, since the difference in viscosity depending on the storage temperature of the water-in-oil emulsion composition can be further reduced.
Examples of the chelating agent include disodium edetate, trisodium edetate, tetrasodium edetate, and dipotassium edetate. It is preferable to use trisodium edetate. A commercially available Kirest 2C-SD manufactured by Kirest Co., Ltd. can be used.
The water-in-oil emulsion composition preferably contains 0.0001% by mass to 0.2% by mass of a chelating agent.

  In the water-in-oil emulsion composition of the present invention, components that are usually used in cosmetics, for example, nonionic surfactants, anionic surfactants, as long as the effects of the present invention are not impaired as optional components Agents, cationic surfactants, amphoteric surfactants, oil agents, polyhydric alcohols and other moisturizers, thickeners, antioxidants, UV absorbers, salts, pH modifiers, antiseptics, antibacterial agents, colorants Perfumes and the like can be blended. In addition, cosmetic ingredients such as ascorbic acid derivatives, ceramides, and plant extracts can be blended.

Examples of the oil agent include fats and oils such as ester oil and vegetable oil, hydrocarbons, higher fatty acids, higher alcohols, and silicone oils.
Examples of ester oils include cetyl ethylhexanoate, 1,3-butylene glycol diisononanoate, 1,3-butylene glycol di-2-ethylhexanoate, dipropylene glycol diisononanoate, dipropylene glycol di-2-ethylhexanoate, Examples include isononyl isononanoate, glyceryl tri-2-ethylhexanoate, glyceryl tricaprate, glyceryl triisostearate, neopentyl glycol dicaprate, ethylhexyl palmitate, isostearyl neopentanoate, and the like.
Examples of the fats and oils include camellia oil, evening primrose oil, macadamia nut oil, olive oil, rapeseed oil, corn oil, sesame oil, jojoba oil, germ oil, wheat germ oil, and other liquid oils, cocoa butter, coconut oil, and hardened coconut oil. , Solid oils such as palm oil, palm kernel oil, mole owl, owl kernel oil, hydrogenated oil, hydrogenated castor oil, waxes such as beeswax, candelilla wax, cotton wax, nuka wax, lanolin, lanolin acetate, liquid lanolin, sugarcane wax Is mentioned.
Examples of the hydrocarbons include liquid paraffin, squalene, squalane, and microcrystalline wax.
Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, docosahexaenoic acid (DHA), eicosapentaenoic acid (EPA), and the like.
Examples of the higher alcohol include linear alcohols such as lauryl alcohol, stearyl alcohol, cetyl alcohol, and cetostearyl alcohol, branched alcohols such as monostearyl glycerin ether, lanolin alcohol, cholesterol, phytosterol, and octyldodecanol. .
Examples of the silicone oil include linear polysiloxanes such as dimethylpolysiloxane and methylphenylpolysiloxane, cyclic polysiloxanes such as decamethylcyclopentasiloxane, cyclopentasiloxane, and (dimethicone / vinyl dimethicone) crosspolymer.
Examples of the humectant include glycerin, diglycerin, 1,3-butylene glycol, dipropylene glycol, and pentylene glycol.
Examples of the thickener include (dimethicone / vinyl dimethicone) crosspolymer.
Examples of the salts include sodium chloride and magnesium sulfate.
Examples of the pH adjusting agent include citric acid, sodium citrate, phosphoric acid, sodium phosphate, potassium hydroxide and the like.
Examples of the preservative include phenoxyethanol and paraben.
Examples of the ascorbic acid derivative include L-ascorbic acid phosphate magnesium salt, L-ascorbic acid phosphate sodium salt, 2-O-α-D-glucopyranosyl-L-ascorbic acid and the like.
Examples of ceramide include cetyl PG hydroxyethyl palmitate, cerebroside and the like.

  The water-in-oil emulsified composition of the present invention can be used as a quasi-drug or pharmaceutical as cosmetics such as milky lotion, cream, cosmetic liquid, sunscreen, liquid foundation, etc., or as a skin external preparation.

〔Example〕
In the compositions of Tables 1, 2, and 3, water-in-oil emulsion compositions of Examples 1 to 10 and Comparative Examples 1 to 17 were prepared by the following preparation method.

(Preparation method)
The oil phase and the water phase are separately heated to 80 ° C. and sufficiently stirred, and then the water phase is added to the oil phase, emulsified by stirring at 6000 rpm for 2 minutes with a homomixer, and then stirred and cooled to room temperature. In addition, (A) component of this invention is mix | blended with an oil phase, and (B) component is mix | blended with an aqueous phase.

[Evaluation of water-in-oil emulsion composition]
The viscosity was measured about the water-in-oil type emulsion composition of Examples 1-10 and Comparative Examples 1-17, and the emulsification state was observed with the microscope. Details of the measurement method and the like are shown below.

(Viscosity the day after the prototype)
The obtained water-in-oil emulsion composition was filled in a glass container having a diameter of about 3 cm and stored at 25 ° C., and the viscosity of the day after preparation was measured (B-type viscometer, No. 4, rotor, 12 rpm, 30 seconds).

(Viscosity at storage temperature)
The obtained water-in-oil emulsion composition was filled into a glass container having a diameter of about 3 cm, stored at 5 ° C., 25 ° C., 40 ° C., and 50 ° C. for 7 days. Measurement (B-type viscometer, No. 4, rotor, 12 rpm, 30 seconds) was performed.

(Viscosity when returned from storage temperature to room temperature)
The obtained water-in-oil emulsion composition was filled into a glass container having a diameter of about 3 cm, stored at 5 ° C., 25 ° C., 40 ° C., and 50 ° C. for 7 days. The viscosity was measured (B-type viscometer, No. 4, rotor, 12 rpm, 30 seconds).

When the difference in viscosity between room temperature (25 ° C) and each storage temperature (5 ° C, 40 ° C, 50 ° C) is small, the feeling of use (viscosity) is always constant without being affected by the environment (outside temperature) during use. It was determined that a water-in-oil emulsion composition could be provided.
In order to evaluate the change in viscosity due to storage temperature, the ratio of the viscosity of each storage temperature (5 ° C., 40 ° C., 50 ° C.) to room temperature (25 ° C.) was calculated according to the following formula. The closer the value is to 1, the better the emulsion composition with less change in viscosity.
Viscosity ratio A = Viscosity at each storage temperature ÷ 25 ° C viscosity

Similarly, for the viscosity when the storage temperature was returned to room temperature (25 ° C.), the ratio of the viscosity was calculated by the following formula. The closer the value is to 1, the better the emulsified composition that the composition does not change with storage temperature.
Viscosity ratio B = viscosity when each storage temperature is returned to room temperature / viscosity of 25 ° C.

(Microscopic observation)
The water-in-oil emulsion composition stored at 25 ° C. for 1 day was observed with a system polarization microscope BX-50-33P-D manufactured by OLYMPUS at a magnification of 400 and judged according to the following criteria.
◎: Particle size is fine and uniform ○: Particle size is not fine but uniform △: Particle size is uneven ×: Particle size is not uniform and unification is seen

In addition, in the composition of Tables 1-3, what was given * mark beside the ingredient name shows that the following commercial item was used.
* 1 “Cisroll DPHS” manufactured by Croda Japan Co., Ltd.
* 2 “Vitamin E sodium phosphate” manufactured by Showa Denko KK
* 3 “El Dew APS-307” manufactured by Ajinomoto Co., Inc.
* 4 “KSG-15” manufactured by Shin-Etsu Chemical Co., Ltd.
* 5 Ciba Japan Co., Ltd. “Tinocare Gl”
* 6 “Kiretos 2C-SD” manufactured by Kiretos Co., Ltd.
* 7 “ISOLAN GPS” manufactured by Evonik Degussa Japan
* 8 “NIKKOL Hexaglyn PR-15” manufactured by Nikko Chemicals Corporation
* 9 "NIKKOL DGMIS" manufactured by Nikko Chemicals Co., Ltd.
* 10 Protecil FN manufactured by Seiwa Kasei Co., Ltd.
* 11 “Penator GE-IS” manufactured by Kao Corporation
* 12 “Exepar IS-CE-A” manufactured by Kao Corporation

The results of evaluating the water-in-oil emulsion composition of the present invention are shown in Table 1.
In addition, the minus (-) in a table | surface represents not having measured, and x represents having been unable to emulsify.

The emulsified composition of Comparative Example 1 emulsified with component (A), dipolyhydroxystearic acid PEG-30, had a viscosity of 2100 mPa · s, which was a lower viscosity.
(A) Lipophilic thickener (hydrogenated polyisobutene, palmitic acid) generally used as a thickener for cosmetics in a water-in-oil emulsion composition emulsified with PEG-30, a dipolyhydroxystearic acid component Dextrin, (behenic acid / eicosanedioic acid) glyceryl, (dimethicone / vinyl dimethicone) crosspolymer, and hydrophilic thickener (xanthan gum, sclerotium gum) were blended, but the thickening effect was low ( Comparative Examples 4, 5, 7-13).
Comparative Example 5 blended with (dimethicone / vinyl dimethicone) crosspolymer, which is a lipophilic thickener, blended with (dimethicone / vinyl dimethicone) crosspolymer, which is a lipophilic thickener, and glyceryl (behenic acid / eicosanedioic acid) Comparative Example 9 has a relatively thickened composition in this test, but the viscosity of the obtained water-in-oil emulsion composition is 4500 mPa · s, and the composition of Comparative Example 1 does not contain a thickener. The viscosity could only be increased up to about twice the 2100 mPa · s of the product.

Comparative Example 3 and Comparative Example 6 contain neither a hydrophilic thickener nor a lipophilic thickener, and contain magnesium sulfate, L-ascorbyl magnesium salt, citric acid and potassium hydroxide as the electrolyte.
This is a test carried out based on the knowledge that the water-in-oil emulsion composition increases the viscosity when an electrolyte is included.
The viscosity of Comparative Example 3 in which magnesium sulfate was blended was 2850 mPa · s, and the viscosity of Comparative Example 6 in which L-ascorbyl phosphate magnesium salt and potassium hydroxide were blended was 4500 mPa · s. I couldn't.
On the other hand, Examples 1-5 which mix | blended sodium tocopheryl phosphate have high viscosity with 14550 mPa * s, 11400 mPa * s, 21600 mPa * s, 7600 mPa * s, and 16750 mPa * s, respectively.
When Example 1 using a common oil agent and Comparative Examples 3 to 12 are compared, it can be seen that the viscosity increases 3 to 10 times by adding sodium tocopheryl phosphate.
Examples 1 to 5 are not sticky and have a refreshing feeling as in Comparative Examples 1 to 5, 11 and 12, but the viscosity is increased while maintaining the feeling of use, and the feeling of use is excellent. A high-quality cream was realized. Furthermore, Comparative Examples 6-8, which are inferior in viscosity, were rather sticky to use due to the influence of the lipophilic thickener.

Comparative Example 2 containing no component (A) was not emulsified. When observed on the 14th day, the water-in-oil emulsified composition of Comparative Example 1 not containing (Component B) was separated from the one stored at 50 ° C.
Examples 1 to 5 were stable without separation at all storage temperatures (5 ° C, 25 ° C, 40 ° C, 50 ° C) even after 30 days of storage.
The water-in-oil emulsion composition of Example 2 in which the composition of the present invention further contained trisodium edetate as the chelating agent of component (C) had the smallest difference in viscosity depending on the storage temperature.
To provide a skin external preparation with a constant feeling of use (viscosity) without being affected by the use environment when the environment during use is assumed to be severe (the outside air temperature is low or high). It has been found that it is effective to further contain a chelating agent in the constitution of the present invention.

  Next, the water-in-oil emulsion compositions of Examples 6 to 10 were prepared with the composition shown in Table 2 in which sodium tocopheryl phosphate as the component (B) was added to the composition of Comparative Example 1. This is an experiment for examining how the difference in the blending amount of sodium tocopheryl phosphate as the component (B) affects the viscosity. The results are shown in Table 2.

  When the amount of sodium tocopheryl phosphate was increased, the viscosity increased accordingly (Examples 6 to 10).

Water-in-oil emulsion compositions of Comparative Examples 14 to 17 were prepared with the compositions shown in Table 3.
This test is a water-in-oil emulsion composition that does not contain dipolyhydroxystearic acid PEG-30 as component (A) and combines other surfactants with sodium tocopheryl phosphate as component (B). This was done to confirm the viscosity of The surfactant used in this test is commercially available for preparing a water-in-oil emulsion composition.
The results are shown in Table 3.

The water-in-oil emulsified compositions of Comparative Examples 14 and 15, which do not contain dipolyhydroxystearic acid PEG-30 and are combined with other surfactants and sodium tocopheryl phosphate, were emulsified but had a low viscosity for 1 day. Separated later.
Comparative Examples 16 and 17 were not emulsified.

From the above, the viscosity of the water-in-oil emulsion composition is maintained while maintaining a refreshing feeling without stickiness by combining the dipolyhydroxystearic acid PEG-30 of the present invention and sodium tocopheryl phosphate. It was found that it can be increased.
It was also found that this thickening action is a unique phenomenon due to the combination of dipolyhydroxystearate PEG-30 and sodium tocopheryl phosphate.
The water-in-oil emulsion composition comprising the PEG-30 dipolyhydroxystearate of the present invention and sodium tocopheryl phosphate has an excellent feeling of use without a dull film feeling and a high-class feeling with high viscosity. I was able to realize a cream with.
The water-in-oil emulsion composition having an increased viscosity according to the present invention has a small difference in viscosity depending on the storage temperature, and is therefore useful as an external preparation for skin such as an emulsion or cream.
From the results of Tables 1 and 2, in the examples, the next day viscosity is 7500 to 22000 mPa · s, 6200 to 22000 after the passage of room temperature for 7 days, and no significant fluctuation is observed. The viscosity change is 1.5 to 0.8 and is stable when it is returned to room temperature (25 ° C.), which is the use temperature, after undergoing a temperature environment change considering transportation and storage.
Low temperature hysteresis tends to increase viscosity, and high temperature hysteresis tends to decrease viscosity. When it is returned to 25 ° C. after 5 ° C., it is 8000 to 22850 mPa · s, and when it is returned from 50 ° C. to 25 ° C., it is 6300 to 18900 mPa · s. If it is this range, a fixed quality can be provided with respect to a consumer.
On the other hand, the viscosity is 5000 mPa · s in the comparative example, and is 2.7 to 0.5 when stored at a constant temperature for 7 days, and 1.9 to 0.4 when returned to room temperature. It can be seen that the viscosity stability due to the change is lacking.

Formulation Example 1 Emulsion
(Compounding ingredients) (mass%)
1. Dipolyhydroxystearic acid PEG-30 1
2. Myristoylmethyl-β-alanine (phytosteryl / decyltetradecyl) 2
3. Olive oil 5
4). Jojoba oil 4
5. Ethyl hexyl palmitate 3
6). Cetyl PG hydroxyethyl palmitamide 0.5
7). Triethylhexanoin 1
8). (Dimethicone / Vinyl Dimethicone) Cross Polymer 1
9. Glycerin 5
10. Pentylene glycol 2
11. Phenoxyethanol 0.2
12 Sodium tocopheryl phosphate 3
13. Purified water residue

(Manufacturing method)
The oil phase (1-8) and the water phase (9-13) are separately heated to 80 ° C. and sufficiently stirred, and then the water phase is added to the oil phase and emulsified by stirring at 6000 rpm for 2 minutes with a homomixer. Then, the mixture is stirred and cooled to room temperature.

  The emulsion of Formulation Example 1 had a pleasant feeling of use and was excellent in storage stability.

Formulation Example 2 Cream
(Compounding ingredients) (mass%)
1. Dipolyhydroxystearic acid PEG-30 2
2. Myristoylmethyl-β-alanine (phytosteryl / decyltetradecyl) 2
3. Olive oil 3
4). Jojoba oil 1
5. Ethyl hexyl palmitate 2
6). Cetyl PG hydroxyethyl palmitamide 0.5
7). Cetyl 2-ethylhexanoate 1
8). Dimethicone 1
9. Diglycerin 5
10. Pentylene glycol 2
11. Phenoxyethanol 0.2
12 Sodium tocopheryl phosphate 3
13. Purified water residue

(Manufacturing method)
The oil phase (1-8) and the water phase (9-13) are separately heated to 80 ° C. and sufficiently stirred, and then the water phase is added to the oil phase and emulsified by stirring at 6000 rpm for 2 minutes with a homomixer. Then, the mixture is stirred and cooled to room temperature.

  The cream of Formulation Example 2 had a pleasant feeling of use and was excellent in storage stability.

Claims (4)

A water-in-oil emulsion composition comprising PEG-30 dipolyhydroxystearate as component (A) and sodium tocopheryl phosphate as component (B). Furthermore as component (C), water-in-oil emulsion composition according to claim 1, characterized in that it contains a chelating agent. The water-in-oil type according to claim 1 or 2 , wherein the viscosity by stirring with a B-type viscometer, No. 4 rotor, 12 rpm, 30 seconds at a measurement temperature of 25 ° C is in the range of 5000 to 22000 mPa · s. Emulsified composition. The blending amount of component (A) dipolyhydroxystearic acid PEG-30 is 0.1 to 5% by mass, and the blending amount of component (B) sodium tocopheryl phosphate is 0.1 to 10% by mass. The water-in-oil emulsion composition according to any one of claims 1 to 3 .